EP1057854B1 - Méthode de recyclage de résines de styrène usagées - Google Patents

Méthode de recyclage de résines de styrène usagées Download PDF

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Publication number
EP1057854B1
EP1057854B1 EP00111407A EP00111407A EP1057854B1 EP 1057854 B1 EP1057854 B1 EP 1057854B1 EP 00111407 A EP00111407 A EP 00111407A EP 00111407 A EP00111407 A EP 00111407A EP 1057854 B1 EP1057854 B1 EP 1057854B1
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Prior art keywords
styrene resin
resin material
waste
combustion
retardant agent
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EP00111407A
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German (de)
English (en)
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EP1057854A3 (fr
EP1057854A2 (fr
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Tsutomu Noguchi
Mayumi Miyashita
Miyuki Kamei
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Sony Corp
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Sony Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • This invention relates to a method for recycling a high-quality regenerated styrene resin from a waste styrene resin, such as expanded styrene or styrene cabinets, or waste styrene resin doped with a combustion-retardant agent, such as expanded styrene or styrene cabinets doped with a combustion-retardant agent.
  • a waste styrene resin such as expanded styrene or styrene cabinets
  • a combustion-retardant agent such as expanded styrene or styrene cabinets doped with a combustion-retardant agent.
  • the styrene resins doped or not doped with a combustion-retardant agent, is used extensively as a cabinet material for a variety of electric equipment or as a building material.
  • expanded styrene is used in large quantities as a variety of packaging materials.
  • the above-described recycling system suffers a problem that the solvent which has dissolved the expanded styrene or styrene cabinets in the regenerated styrene be left over in the regenerated styrene. If the organic solvent is left over in the regenerated styrene, its heat resistance or tensile strength is appreciably lowered to degrade the quality of the regenerated styrene. In particular, ester-based solvents are high boiling such that the solvent is liable to be left over even on heating in vacuum for removing volatile components. If the heating temperature is raised to lower the amount of the residual solvent, the styrene resin tends to be thermally decomposed to lower the strength of the styrene material.
  • a heating step is included in the recycling process, such that, if the recycling process is carried out in vacuum, oxidation is produced under the effect of residual oxygen, such that the molecular weight of the regenerated styrene resin is decreased. If the molecular weight is decreased, the regenerated materia is lowered in tensile strength and impact strength, thus appreciably lowering its quality.
  • expanded styrene doped with a combustion-retardant agent used as a building material, or expanded styrene doped with a combustion-retardant agent, used as a cabinet for a television receiver, contains a halogen-based combustion-retardant agent in an amount approximately 1 to 10 wt%. If the styrene resin containing the combustion-retardant agent is heated to a temperature of 200°C or higher, the combustion-retardant agent is thermally decomposed to yield an acid which leads to significantly lowered strength of the styrene resin and hence to significantly lowered quality of the regenerated styrene.
  • combustion-retardant agent halogen-based combustion-retardant agents are used as a rule, so that dioxins are feared to be produced in the course of incineration for disposal.
  • the present invention provides a method for recycling a waste styrene resin material including dissolving the waste styrene resin material in an organic solvent boiling at a temperature lower than 200°C and having solubility not less than 15 wt% at room temperature to prepare a solution of the waste styrene resin material, removing impurities from the solution of the waste styrene resin material; and vacuum heating the solution of the waste styrene resin material freed of the impurities to remove volatile components and the organic solvent to reduce the amount of the residual solvent in the styrene resin to not larger than 0.4 wt% to recycle the resulting styrene resin as a regenerated styrene resin.
  • the waste styrene resin material is dissolved in an organic solvent boiling at a temperature lower than 200°C and having solubility not less than 15 wt% at room temperature, the amount of the organic solvent used is diminished to improve the operating efficiency.
  • the amount of the residual solvent in the styrene resin is 0.4 wt% or less, characteristics of the material of the regenerated styrene resin, such as the thermal resistance or tensile strength, may be maintained at optimum values.
  • the present invention provides a method for recycling a waste styrene resin material doped with a combustion-retardant agent including dissolving the waste styrene resin material doped with the combustion-retardant agent in an organic solvent boiling at a temperature lower than 200°C and having solubility not less than 15 wt% at room temperature to prepare a solution of the waste styrene resin material, removing the combustion-retardant agent from the solution of the waste styrene resin material to give an amount of the residual combustion-retardant agent in the styrene resin to not larger than 1 % and vacuum heating the solution of the waste styrene resin material freed of the combustion-retardant agent to remove the volatile components and the organic solvent to reduce the amount of the residual solvent in the styrene resin to not larger than 0.4 wt% to recycle the resulting styrene resin as a regenerated styrene resin.
  • the waste styrene resin material doped with the combustion-retardant agent is dissolved in an organic solvent boiling at a temperature lower than 200°C and having solubility not less than 15 wt% at room temperature, the amount of the organic solvent used is diminished to improve the operating efficiency.
  • the amount of the residual solvent in the styrene resin is 0.4 wt% or less, characteristics of the material of the regenerated styrene resin, such as the thermal resistance or tensile strength, may be maintained at optimum values.
  • the amount of the residual solvent in the styrene resin may be set to 0.4 wt% or less, the amount of the acid yielded on thermal decomposition of the combustion-retardant agent may be diminished to affect the strength of the material of the regenerated styrene resin only to a lesser extent to evade attacking the processing equipment.
  • the amount of the organic solvent used may be diminished to improve the operating efficiency.
  • characteristics of the material of the regenerated styrene resin such as thermal resistance or tensile strength, may be maintained at optimum values. This renders it possible to recycle the high-quality regenerated styrene resin.
  • the amount of the organic solvent used may be diminished to improve the operating efficiency.
  • characteristics of the material of the regenerated styrene resin such as thermal resistance or tensile strength, may be maintained at optimum values.
  • the amount of the residual combustion-retardant agent may be not larger than 1%, the amount of the acid yielded on thermal decomposition of the combustion-retardant agent may be diminished to eliminate adverse effects of the regenerated styrene resin on the strength of the resin material or on the processing equipment.
  • the added value of the regenerated styrene resin doped or not doped with the combustion-retardant agent and the application may be raised to reduce the waste material to save natural resources and energy.
  • the present invention resides in that a waste material of styrene resin, such as expanded styrene or styrene cabinets, is dissolved in an organic solvent for decreasing the volume of the waste material, the resulting solution is transported to a recycling plant and heated in vacuum to remove volatile components and the organic solvent to recycle the residual produce as regenerated styrene, in which the power of dissolution and the boiling point of the organic solvent as well as the residual solvent in the regenerated styrene are prescribed to recycle the regenerated styrene of high quality.
  • the articles processed according to the present invention are waste materials of styrene resins in general, irrespective of the configuration or properties thereof, such as packaging materials of expanded styrene, fish boxes of expanded styrene, a variety of styrene cabinets.
  • the organic solvent used is such an organic solvent which has a power of dissolution of not less than 15 wt% at ambient temperature and a boiling point of 200°C or lower.
  • organic solvent dissolving the waste styrene resin an organic solvent having the power of dissolution of not less than 15 wt% at ambient temperature is used, it is possible to decrease the amount of the organic solvent used, while it is also possible to improve the working efficiency in the vacuum heating process aimed at removing volatile components.
  • organic solvent dissolving the waste styrene resin an organic solvent, an organic solvent boiling at 200°C or lower is used, it is possible to improve the operating efficiency in the vacuum heating process aimed at removing volatile components, while it is possible to decrease the amount of the residual solvent in the styrene resin reliably.
  • Examples of usable organic solvents include ketone-based and mono-terpene based organic solvents.
  • halogen-free organic solvents such as toluene, d-limonene, ethyl benzene, tetrahydrofuran, methylethylketone and monoterpene-based solvents.
  • d-limonene is an organic solvent favorable for this usage. This d-limonene is a vegetable oil extracted from the rind of oranges and is used as a food additive. It is high in safety factor and dissolving power for the expanded styrene such that it is optimum as a solvent used in the present invention.
  • the residual solvent in the styrene resin appreciably lowers characteristics of the material, such as thermal resistance or tensile strength of the regenerated styrene resin to lower its tensile strength and hence the quality of the material significantly.
  • the recycled styrene resin is worked into regenerated styrene pellets with a diameter and a length each of the order of 3 mm.
  • the residual solvent in the.regenerated styrene pellets are left unchanged in a product manufactured from the pellets. If the residual solvent is present in large quantities in the regenerated styrene pellets, the material of a product obtained using the pellet is lowered in properties to lower the product quality.
  • the amount of the residual solvent in the styrene resin is desirably o.4 wt% or less. If the amount of the residual solvent in the styrene resin is not less than 0.4 wt%, the properties of the material of the regenerated styrene resin, such as resistance to heating or tensile strength, are appreciably lowered to deteriorate the product quality. Thus, by setting the amount of the residual solvent in the styrene resin to 0.4 wt% or less, it is possible to recycle high-quality regenerated styrene having good characteristics.
  • the recycling process for the styrene resin includes a hot-working step, such that, even if recycling is repeated in vacuum, the styrene resin is oxidized under the effect of residual oxygen to lower the molecular weight of the regenerated styrene resin. If the molecular weight is decreased, the tensile strength or the impact strength is lowered to give rise to the appreciably lowered product quality. It is therefore desirable to add an anti-oxidant to a styrene resin solution, before proceeding to the hot-working step, in order to prevent oxidation of the regenerated styrene resin. The reason is that, when heat is applied to the styrene resin during the hot-working step, the styrene resin is oxidized to prevent the molecular weight from being decreased.
  • anti-oxidants phosphorus-based, phenolic and sulfuric oxides are extensively used. If a vacuum heating step is executed, it is desirable to use anti-oxidants having a low vapor pressure.
  • hindered phenolic anti-oxidants are preferentially used.
  • 0.01 to 0.5 wt% of the hindered phenolic anti-oxidants is added based on the weight of the waste material of the styrene resin.
  • the hindered phenolic anti-oxidants are preferably of a vapor pressure at 20°C equal to 10 -7 Pa or less.
  • the anti-oxidants having a low vapor pressure are especially high in its effect in prohibiting oxidation of the styrene resin, such that, by using those anti-oxidants, the number of times of recycling can be increased further.
  • the heating temperature used in executing vacuum heating for removal of volatile components is preferably less than 260°C. If the heating temperature is not less than 260°C, the styrene resin is thermally decomposed to appreciably lower the characteristics of the material of the regenerated styrene resin, such as thermal resistance or tensile strength, as well as to significantly decrease the molecular weight of the regenerated styrene resin to lower the product quality significantly. If the heating temperature used in executing the vacuum heating for removing volatile components is set to 260°C or less, it is possible to maintain optimum characteristics of the material of the styrene resin to recycle the high-quality styrene resin.
  • Fig. 1 shows the processing flow in recycling the waste styrene resin material.
  • a waste styrene resin material 1 is crushed and pulverized at 2 and dissolved in an organic solvent in a dissolution tank 3 to provide a homogeneous composition.
  • This homogenized solution is continuously freed of a combustion-retardant agent, as a non-soluble component, in a decanter 4, as the solution is heated to a temperature of the order of 60°C.
  • the clarified solution is sent to a filtration unit 5 where it is filtered and subsequently separated into a styrene resin and the solvent in a separator 6.
  • This separator 6 is heated to approximately 240°C by e.g., the heat medium of the boiler 7.
  • This separated styrene resin is cooled by a cooler 9, on actuating a gear pump 8, and processed by a pelletizer 10 to produce regenerated pellets 11 which then are transported to a molding plant for re-utilization as a variety of molded products or polystyrene vessels.
  • the vapor of a solvent separated by the separator 6 is liquefied by a condenser 12 and recovered as a regenerated solvent (regenerated limonene) in a tank for the regenerated solvent 13.
  • the present invention resides in a recycling system for styrene in which a waste material of styrene resin, such as expanded styrene doped with a combustion-retardant agent or styrene cabinets doped with a combustion-retardant agent, is dissolved in an organic solvent for reducing the volume of the waste material and freed of the combustion-retardant agent, with the resulting solution being transported to a recycling plant for heating in vacuum for removing volatile components and recovering the organic solvent, with the resulting product being recycled as regenerated styrene.
  • the power of dissolution and the boiling point are prescribed to recycle the high-quality regenerated styrene.
  • the object of processing is the waste styrene resin material doped with the combustion-retardant agent as a whole, such as, for example, expanded styrene packaging material, doped with a combustion-retardant agent, an expanded styrene fish box, the material of which is doped with a combustion-retardant agent, or a variety of styrene cabinets, the material of which is doped with a combustion-retardant agent, irrespective of the material configuration or shape.
  • the combustion-retardant agent as a whole, such as, for example, expanded styrene packaging material, doped with a combustion-retardant agent, an expanded styrene fish box, the material of which is doped with a combustion-retardant agent, or a variety of styrene cabinets, the material of which is doped with a combustion-retardant agent, irrespective of the material configuration or shape.
  • the waste styrene resin material, doped with the combustion-retardant agent, is dissolved in an organic solvent.
  • the waste styrene resin material, doped with the combustion-retardant agent is preferably pulverized to a size of the order of 1mm. By such pulverization, it is possible to elevate the speed of dissolution in the organic solvent.
  • the solution obtained on dissolving the waste styrene resin material doped with the combustion-retardant agent in the organic solvent is freed of non-soluble components of the combustion-retardant agent, using decantation and filtration.
  • the styrene resin containing a few wt% of the combustion-retardant agent is heated to 200°C or higher, the combustion-retardant agent is thermally decomposed to yield an acid.
  • characteristics of the material of the regenerated styrene resin such as thermal resistance or tensile strength, are appreciably lowered to deteriorate the properties of the material significantly.
  • the processing equipment is attacked with acid yielded on thermal decomposition of the combustion-retardant agent.
  • the amount of the residual combustion-retardant agent in the styrene resin is preferably not larger than 1 wt%. If the amount of the residual combustion-retardant agent in the styrene resin is larger than 1 wt%, the characteristics of the material of the regenerated styrene resin, such as thermal resistance or tensile strength, are appreciably lowered to deteriorate the properties of the material significantly, while the processing equipment is attacked by acid as described above.
  • the amount of the residual combustion-retardant agent in the styrene resin is set so as to be not larger than 1 wt%, it is possible to maintain desirable characteristics of the material of the regenerated styrene resin to prevent corrosion of the processing equipment. Since the rate of yielding of the acid becomes the higher the higher the heating temperature, the heating temperature used for vacuum heating for removing volatile components is preferably less than 260°C taking also the deterioration of the styrene resin into consideration. By setting the heating temperature so as to be less than 260°C, it is possible to suppress the yielding of the acid to prevent adverse effect of the regenerated styrene resin on the characteristics of the material and the processing equipment.
  • the processing for removing the combustion-retardant agent prior to the heating process can be performed using the decantation.
  • the decantation it is possible to remove the waste styrene resin material doped with the combustion-retardant agent present as a non-soluble component in the solution on dissolving the waste styrene resin material-doped with the combustion-retardant agent in the organic solvent.
  • the amount of the residual combustion-retardant agent in the styrene resin following combustion-retardant agent removal can be decreased.
  • the amount of the combustion-retardant agent present as a non-soluble component in the solution can be increased, thus increasing the amount of the combustion-retardant agent removed at the time of the processing for removing the combustion-retardant agent using the decantation to diminish the amount of the residual combustion-retardant agent in the styrene resin.
  • the processing for removing the combustion-retardant agent can also be performed using a centrifugal separator.
  • the combustion-retardant agent can also be removed by precipitating the styrene resin by mixing a lower alcohol in the solution in which is dissolved the waste styrene resin material doped with the combustion-retardant agent. Since the styrene resin is dissolved in this case as a non-soluble component, it can be separated from the combustion-retardant agent dissolved in the solution. It is possible in this manner to separate the styrene resin and the combustion-retardant agent effectively from each other to diminish the amount of the residual combustion-retardant agent in the styrene resin.
  • the lower alcohol preferably has a boiling point lower than 200°C.
  • the lower alcohol preferably has the number of carbon atoms not less than two in view of its effect on the human body and inflammability. If the solubility differential between the combustion-retardant agent and the styrene resin is taken into account, the number of carbon atoms in the lower alcohol of 2 to 5 is preferred.
  • the lower alcohol may be enumerated by ethanol, propanol, butanol and pentanol.
  • the combustion-retardant agent may also be removed first by decantation or centrifugation followed by mixing of the lower alcohol into the solution for precipitation of the styrene resin. This enables the styrene resin and the combustion-retardant agent to be removed more reliably from each other to lower the amount of the residual combustion-retardant agent in the regenerated styrene resin.
  • Fig.2 shows an illustrative flow diagram for recycling the waste styrene resin material doped with the combustion-retardant agent.
  • the waste styrene resin material doped with the combustion-retardant agent 21 is crushed and pulverized at 22 and dissolved in a dissolution tank A23 in the organic solvent to give a homogeneous composition.
  • This homogeneous composition heated to a temperature of approximately 60°C, is continuously freed of the combustion-retardant agent as a non-soluble component, in a decanter 24.
  • the clarified solution is separated in the separator 25 into the styrene resin and the solvent.
  • This separator 25 is heated to approximately 240°C by a heat medium, such a boiler 26.
  • the separated styrene resin is cooled through a cooler 28 by the driving of a gear pump 27 and processed by a pelletizer 29 to form regenerated pellets 30 which then are transported to a molding plant to produce various molded products and polystyrene vessels for re-use.
  • a condenser 31 which then is recovered as a regenerated solvent (regenerated limonene) in a tank for regenerated limonene 32.
  • the homogeneous solution, obtained on dissolution in the organic solvent in the solution tank A 23, may be transferred to a solution tank B for mixing into a lower alcohol.
  • styrene resin precipitates 33 are generated as a non-soluble component for separation into the styrene resin and the solvent.
  • the separated styrene resin precipitates 33 are fed to a separator 25 and recycled by a process similar to that described above
  • the separated styrene resin precipitates 33 may also sent to a vacuum heating extruder 34 for extrusion into a yarn-like product which may then be sent to a cooler 28.
  • the solution clarified by the decanter 24 may also be sent into a solution tank B for recycling by a process similar to one described above.
  • experimental examples 1 to 7 show experimental examples of the methods for recycling the waste styrene resin material.
  • the vacuum heating for removing volatile components was carried out under the following conditions:
  • the amount of the residual solvent in the regenerated styrene pellets in each case was not larger than 0.1 wt%.
  • the rate of decrease of the molecular weight of the regenerated styrene pellets in each case was not larger than 5%.
  • the tensile strength, impact strength and the softening point were measured. The results are shown in Table 1: after recycling new resin tensile strength (kg/cm 2 ) 473 479 bending strength (kg/cm 2 ) 710 720 impact strength (kgfm/cm) 0.8 0.7 softening point (°C) 103.4 103.5
  • a 30 wt% solution of expanded styrene in d-limonene was prepared to prepare regenerated styrene pellets in the same way as in the Experimental Example 1.
  • the degree of vacuum in the vacuum chamber was changed to change the amount of the residual solvent in the regenerated styrene pellets in a range of from 0.0 to 1.1% to prepare seven samples of the regenerated styrene pellets to check into thermal resistance of each sample.
  • the thermal resistance was evaluated by measuring the glass transition temperature Tg as an index of the thermal resistance.
  • the thermal resistance of the styrene pellets by the amount of the residual solvent in the regenerated styrene pellets was checked as in the experimental example 2.
  • the degree of vacuum in the vacuum chamber was changed to change the amount of the residual solvent in the regenerated styrene pellets in a range from 0.045 to 0.6% to fabricate five samples of the regenerated styrene pellets to check the thermal resistance of the respective samples.
  • the thermal resistance was checked by measuring the glass transition temperature Tg as in the experimental example 2. The results are shown in Fig.4.
  • a 30 wt% solution in d-limonene of polystyrene, manufactured by ASAHI KASEI CO. LTD. under the trade name of PS685 was prepared and the hindered phenolic anti-oxidants were added in amounts of 0.1, 0.2 and 0.5 wt% based on the weight of polystyrene to respective solutions.
  • the resulting solutions were heated at 230 ° C for one hour in air to prepare respective samples.
  • IRGANOX 1330 and IRGANOX 3114 having the vapor pressure not higher than 10 -12 Pa, exhibit high effect in preventing the polystyrene molecular weight from being decreased. It has also been seen from this that, by adding the hindered phenolic anti-oxidants in an amount not larger than 0.5 wt% based on the weight of polystyrene, the polystyrene molecular weight can be prevented from being decreased, that is that polystyrene can be prevented from being oxidized.
  • Example 2 ten times of recycling operations were performed in a similar manner to Example 1 except that polystyrene manufactured by ASAHI KASEI CO. LTD. under the trade name of PS685 and d-limonene were used as the polystyrene resin and as the organic solvent, respectively, and that 0.1 wt% of the hindered phenolic anti-oxidants IRGANOX 1330 was added to a polystyrene solution in d-limonene based on the weight of polystyrene in each recycling operation. It was found that the rate of decrease of polystyrene was not higher than 10%. It may be seen from this that, by using the hindered phenolic anti-oxidants IRGANOX1330 with the low vapor pressure, the number of times of recycling can be increased further to render possible more effective utilization of resources.
  • Polystyrene recycling was carried out as in Experimental Example 5 except using polystyrene manufactured by ASAHI KASEI CO. LTD. under the trade name of PS685, using toluene (aromatic organic solvent), methylethylketone (ketonic organic solvent), tetrahydrofuran (etheric solvent), pinene and dipentene (terpene-based organic solvent) and a mixture of these solvents and using hindered phenolic anti-oxidants IRGANOX1330.
  • the rates of decrease of the polystyrene molecular weight after ten times of recycling were not higher than 20%.
  • the heating temperature for vacuum heating for removing volatile components was raised to 260°C for removing volatile components.
  • the amount of the residual solvent in the regenerated styrene pellets was not decreased to below 0.4 wt%. If the heating temperature of the vacuum heating for removing volatile components is raised to 260°C, the regenerated styrene pellets undergo thermal decomposition so that the molecular weight is decreased by 10%, with the color of the pellets being changed to yellow.
  • the heating temperature of the vacuum heating for removing volatile components needs to be lower than 260°C, whilst the organic solvent boiling at lower than 200°C needs to be selectively used.
  • Samples of regenerated styrene pellets were prepared in the same way as in the Experimental Example 1, except that polystyrene manufactured by ASAHI KASEI CO. LTD. under the trade name of PS685 and d-limonene were used as the polystyrene resin and as the organic solvent, respectively, to prepare a polystyrene solution, and that a phosphorus-based anti-oxidant and a sulfur-based anti-oxidant, each having a vapor pressure exceeding 10 -6 Pa, were added to the polystyrene solution in amounts of 0.1, 0.2 and 0.5 wt%, based on the polystyrene weight.
  • the following three sorts of the phosphorus-based anti-oxidant and the sulfur-based anti-oxidant are considered as the regenerated styrene pellets.
  • the waste styrene resin material doped with the combustion-retardant agent which is the waste TV cabinet material containing 10 wt% of decabromo diphenyl ether (bromine-based combustion-retardant agent), was crushed to a size of approximately 1cm.
  • the crushed waste material was pulverized using a mesh mill manufactured by HORAI CO.LTD.
  • the pulverized waste styrene resin material doped with the combustion-retardant agent was dissolved, using a dissolution tank fitted with a stirrer and a temperature adjustment unit, manufactured by MITSUBISHI KAKOKI CO. LTD., so that the amount of the waste styrene resin material will be 30 wt% based on the weight of toluene, d-limonene and dipentene.
  • the resulting solution at 60°C was freed of bromine-based combustion-retardant agent, as a non-soluble component, by centrifugation, using a decanter centrifuge, with a separator plate, manufactured by MITSUBISHI KAKO CO. LTD. under a trade name of DZ20, having a centrifugal force of 3500 G.
  • the solution freed of the combustion-retardant agent was then passed through a back filter with a pore diameter of approximately 100 ⁇ m and freed of volatile components on a recycling test plant manufactured by MITSUI ZOSEN CO. LTD. under the trade name of HI-VISCUS EVAPORATOR, to prepare regenerated styrene pellets.
  • the vacuum heating for removing volatile components was carried out under the following conditions:
  • the amount of the residual solvent in the regenerated styrene pellets in each case was not larger than 0.1 wt%.
  • the amounts of the residual solvent in the regenerated styrene pellets were 1.5 wt%, 1 wt% and 1 wt% in the cases of toluene, d-limonene and dipentene, respectively.
  • the rate of decrease of the molecular weight were less than 15%, 10% and 10%, respectively. Measurements were made of the tensile strength, bending strength, impact strength and the softening point of the regenerated styrene pellets, as mechanical properties.
  • Fig. shows the relationship between the amount of the combustion-retardant agent in the regenerated styrene pellets, molecular weight and the impact strength for the case of using d-limonene. It may be seen from Fig.5 that, if the amount of the combustion-retardant agent in the regenerated styrene pellets is less than 1 wt%, the rate of decrease of the molecular weight is less than 10%, with the rate of decrease of the impact strength being less than 10%.
  • the amount of the residual combustion-retardant agent exceeds 1 wt% to reach 1.5 wt%, the rate of decrease of the impact strength is increased. This is presumably ascribable to the fact that the decomposition of rubber components due to halogen components contained mainly in the combustion-retardant agent becomes significant. It has thus been seen that, if it is desired to maintain good characteristics of the material of the regenerated styrene resin, the amount of the residual combustion-retardant agent in the regenerated styrene pellets needs to be suppressed to within 1 wt%.
  • the degree of vacuum in the vacuum chamber was varied to adjust the residual solvent quantity in the regenerated styrene pellets to 0.045 wt%, 0.1 wt%, 0.15 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt% and to 0.6 wt%, to fabricate eight sorts of the regenerated styrene pellets and thermal resistance thereof were checked.
  • the thermal resistance was evaluated by measuring the glass transition temperature Tg as an index of the thermal resistance.
  • the glass transition temperature equivalent to that of the new material was displayed, such that the thermal resistance of the regenerated styrene pellets was maintained in an optimum state.
  • the glass transition temperature of the regenerated styrene pellets for the amount of the residual solvent in the regenerated styrene pellets of 0.6 wt% is decreased by approximately 10 ° C, such that the thermal resistance of the regenerated styrene pellets was lowered. It may be seen form this that, in order to maintain optimum thermal resistance, the amount of the residual solvent in the regenerated styrene pellets needs to be set to 0.4 wt% or less.
  • a waste styrene resin material doped with the combustion-retardant agent which is the waste TV cabinet material containing 10 wt% of decabromo diphenyl ether (bromine-based combustion-retardant agent), was crushed to a size of approximately 1cm.
  • the crushed waste material was pulverized using a mesh mill manufactured by HORAI CO.LTD.
  • the pulverized waste styrene resin material doped with the combustion-retardant agent was dissolved, using a dissolution tank fitted with a stirrer and a temperature adjustment unit, manufactured by MITSUBISHI KAKOKI CO. LTD., so that the amount of the waste styrene resin material will be 20 wt% based on the weight of d-limonene, to prepare a solution.
  • This solution at 60°C was continuously freed of bromine-based combustion-retardant agent, as a non-soluble component, by centrifugation, using a decanter centrifuge, with a separator plate, manufactured by MITSUBISHI KAKO CO. LTD. under a trade name of DZ20, having a centrifugal force of 3500 G.
  • the solution, thus centrifuged, was dried. It was found that the amount of the residual combustion-retardant agent in the as-dried styrene resin with the combustion-retardant agent was approximately 1 wt%.
  • the solution freed of the bromine-based combustion-retardant agent was charged into four dissolution tanks and 30 vol% of ethanol, isopropyl alcohol, butanol and pentanol, based on the weight of the solution, was mixed in the solution to precipitate the styrene resin component.
  • the gelated styrene resin precipitates were freed of volatile components on a recycling test plant manufactured by MITSUI ZOSEN CO. LTD. under the trade name of HI-VISCUS EVAPORATOR, to prepare regenerated styrene pellets.
  • the vacuum heating for removing volatile components was carried out under the following conditions:
  • the rate of removal of the combustion-retardant agent varied with the types of the lower alcohols mixed into the system, such that, if the lower alcohols mixed were ethanol and isopropyl alcohol, the removal rate was 80%, whereas, if the lower alcohols mixed were butanol and pentanol, the removal rate was 90%.
  • the amount of the residual combustion-retardant agent in the regenerated styrene pellets could be reduced to 0.1 to 0.2 wt% in either cases.
  • the yield of the styrene resin was 60%.
  • the amount of the residual solvent in the regenerated styrene pellets was not larger than 0.1 wt% in either cases. Measurements were made of the tensile strength, bending strength and the softening point, as mechanical properties. It was found that these properties compare favourably with those of the new resin. Thus, it was confirmed that the regenerated styrene resin having characteristics of the material compare with those of the new material could be recycled even in cases wherein the lower alcohols are mixed into the solution obtained on dissolving the styrene resin in an organic solvent to remove the combustion-retardant agent.
  • a rice-cake-like precipitate of the styrene resin obtained in the Experimental Example 10 was freed of volatile components in a recycling experimental plant having a uniaxial screw extruder capable of vacuum heating to prepare regenerated styrene pellets.
  • the vacuum heating for removing volatile components was carried out under the following conditions:
  • the amount of the residual solvent in the regenerated styrene pellets was not larger than 0.4 wt% for any sample.
  • the rate of decrease of the molecular weight of the regenerated styrene pellets was not larger than 5 % for any samples.
  • Measurements were made of the tensile strength, bending strength and the softening point as mechanical properties. It was found that, for any samples, the mechanical properties compare favourably with those of the new materials thus indicating that optimum characteristics were maintained.
  • the solution then was continuously freed of the bromine-based combustion-retardant agent, as a non-soluble component, at room temperature, using a centrifuging machine manufactured by KUBOTA CO. LTD., a micro-mini centrifuging machine with a centrifugal force of 10000 G.
  • the centrifuged solution was dried to give a residual amount of the combustion-retardant agent in the as-dried styrene resin material doped with the combustion-retardant agent was approximately 1 wt%.
  • the solution freed of the bromine-based combustion-retardant agent was charged into three dissolution tanks and 50 vol% of isopropyl alcohol, butanol and pentanol, based on the volume of the solution, to precipitate the styrene resin component.
  • the gelated styrene resin precipitates were freed of volatile components on a vacuum heating for removing volatile components unit manufactured by MITSUI ZOSEN CO. LTD. under the trade name of HI-VISCUS EVAPORATOR, to prepare regenerated styrene pellets.
  • the vacuum heating for removing volatile components was carried out under the following conditions:
  • the rate of removal of the combustion-retardant agent varied with the types of the lower alcohols mixed into the system, such that, if the lower alcohol mixed was isopropyl alcohol, the removal rate was 80%, whereas, if the lower alcohols mixed were butanol and pentanol, the removal rate was 70%.
  • the amount of the residual combustion-retardant agent in the regenerated styrene pellets could be reduced to 0.3 wt% in either cases.
  • the yield of the styrene resin was increased to 95%.
  • the amount of the residual solvent in the regenerated styrene pellets was not larger than 0.1 wt% in either cases. Measurements were made of the tensile strength, bending strength and the softening point, as mechanical properties. It was found that these properties compare favourably with those of the new resin. Thus, it was confirmed that the regenerated styrene resin having characteristics of the material compare favourably with those of the new material could be recycled even in cases wherein the lower alcohols are mixed into a solution obtained on dissolving the styrene resin in an organic solvent to remove the combustion-retardant agent.
  • the styrene resin was decomposed due to oxidation by oxygen on heating and also due to decomposition products of the bromine-based combustion-retardant agent.
  • the molecular weight of regenerated styrene pellets was decreased by approximately 40%, whilst the glass transition temperature was lowered to approximately 10°C to lower the molecular weight of regenerated styrene pellets.
  • the mechanical properties the tensile strength was lowered by.20%, while the impact strength was decreased by approximately 30%. It was found from this that heating needs to be carried out in vacuum and that, if the expanded waste styrene resin material with a combustion-retardant agent is to be recycled, it is necessary to remove the combustion-retardant agent.
  • a waste styrene resin material doped with the combustion-retardant agent which is the waste TV cabinet material containing 10 wt% of decabromo diphenyl ether (bromine-based combustion-retardant agent), was crushed to a size of approximately 1cm.
  • the crushed waste material was pulverized using a mesh mill manufactured by HORAI CO.LTD.
  • the pulverized waste styrene resin material doped with the combustion-retardant agent was dissolved, using a dissolution tank fitted with a stirrer and a temperature adjustment unit, manufactured by MITSUBISHI KAKOKI CO. LTD., so that the amount of the waste styrene resin material will be 20 wt% based on the weight of DBE ester boiling at 210 to 225°C, to prepare a solution.
  • Regenerated styrene pellets were produced in the same way as in the Experimental Example 8 except not removing the combustion-retardant agent.
  • the amount of the residual solvent in the regenerated styrene pellets was not larger than 0.6 wt%, whilst the glass transition temperature was lowered by approximately 30°C.
  • the heating temperature for vacuum heating for removing volatile components e ⁇ was elevated to 260°C to effect for removing volatile components.
  • the amount of the residual solvent in the regenerated styrene pellets was not lower than 0.4 wt%. If the heating temperature of the vacuum heating for removing volatile components is raised to 260°C, the regenerated styrene pellets undergo thermal decomposition, while the styrene resin is deteriorated significantly, so that the molecular weight is decreased by 30%, with the color of the pellets being changed to deep yellow.
  • the heating temperature of the vacuum heating for removing volatile components needs to be lower than 260°C, whilst the organic solvent boiling at lower than 200°C needs to be selectively used and the combustion-retardant agent needs to be remov3d if it is desired to recycle the styrene resin doped with the combustion-retardant agent.
  • An expanded waste styrene resin material doped with the combustion-retardant agent for a building material, containing 5 wt% of decabromo diphenyl ether (bromine-based combustion-retardant agent), was crushed to a size of approximately 1cm.
  • the crushed waste material was pulverized using a mesh mill manufactured by HORAI CO.LTD.
  • Regenerated styrene pellets were produced in the same way as in the Experimental Example 8 except not removing the combustion-retardant agent.
  • the amount of the residual solvent in the regenerated styrene pellets was not larger than 0.1 wt%, whilst the rate of decrease of the molecular weight of the styrene resin ascribable to decomposition product of the bromine-based combustion-retardant agent was approximately 20%. Also, impurities were yielded in an amount of approximately 2% in the styrene resin, whilst the glass transition temperature, that is thermal resistance, was lowered by 10°C, with the impact strength being decreased by approximately 30%.
  • combustion-retardant agent needs to be removed if the expanded styrene doped with a combustion-retardant agent is to be recycled as the characteristics of the regenerated styrene pellets are maintained.

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Claims (17)

  1. Procédé pour le recyclage d'un matériau usagé de résine de styrène comprenant :
    la dissolution du matériau usagé de résine de styrène dans un solvant organique bouillant à une température inférieure à 200°C et ayant un pouvoir de dissolution par rapport à la résine de styrène qui n'est pas inférieur à 15 % en poids à température ambiante afin de préparer une solution du matériau usagé de résine de styrène ;
    l'élimination des impuretés de ladite solution du matériau usagé de résine de styrène ;
    l'addition d'un antioxydant à la solution du matériau usagé de résine de styrène libérée desdites impuretés ;
    le chauffage sous vide de ladite solution du matériau usagé de résine de styrène, libérée desdites impuretés afin d'éliminer les constituants volatils et le solvant organique pour réduire la quantité du solvant résiduel dans la résine de styrène à une valeur d'au plus 0,4 % en poids afin de recycler la résine de styrène résultante comme résine de styrène régénérée.
  2. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 1, dans lequel ledit antioxydant est ajouté dans une quantité de 0,01 à 0,5 % en poids rapporté au poids du matériau usagé de styrène.
  3. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 1, dans lequel ledit solvant organique est exempt d'halogène.
  4. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 1, dans lequel ledit antioxydant est un antioxydant phénolique encombré et ladite solution est chauffée sous vide à une température de chauffage inférieure à 260°C. pour éliminer les constituants volatils.
  5. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 4, dans lequel ledit antioxydant phénolique encombré présente une pression de vapeur à 20°C d'au plus 10-7 Pa.
  6. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 1, dans lequel ledit solvant organique contient au moins 95 % en volume de d-limonène.
  7. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 1, dans lequel ledit matériau usagé de résine de styrène est un matériau usagé de résine de styrène expansée.
  8. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 1, dans lequel ledit matériau usagé de résine de styrène est une résine usagée de styrène de résistance élevée aux chocs.
  9. Procédé de recyclage d'un matériau usagé de résine de styrène dopé avec un agent retardateur de combustion comprenant :
    la dissolution du matériau usagé de résine de styrène dopé avec l'agent retardateur de combustion dans un solvant organique bouillant à une température inférieure à 200°C et ayant une solubilité d'au moins 15 % en poids à température ambiante pour préparer une solution du matériau usagé de résine de styrène ;
    l'élimination de l'agent retardateur de combustion de ladite solution du matériau usagé de résine de styrène pour fournir une quantité de l'agent retardateur de combustion résiduel dans la résine de styrène d'au plus 1 % ;
    l'addition d'un antioxydant à la solution du matériau usagé de styrène ayant une quantité de l'agent retardateur de combustion résiduel dans la résine de styrène d'au plus 1 % ; et
    le chauffage sous vide de ladite solution du matériau usagé de résine de styrène, libérée dudit agent retardateur de combustion afin d'éliminer les constituants volatils et le solvant organique pour réduire la quantité du solvant résiduel dans la résine de styrène à au plus 0,4 % en poids afin de recycler la résine de styrène résultante comme résine. de styrène régénérée.
  10. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 9, dans lequel ledit solvant organique est exempt d'halogène.
  11. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 9, dans lequel un alcool inférieur est ajouté à ladite solution du matériau usagé de résine de styrène afin de faire précipiter la résine de styrène pour fixer la quantité de l'agent retardateur de combustion résiduel à au plus 1 %.
  12. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 9, dans lequel ledit alcool inférieur présente un point d'ébullition inférieur à 200°C.
  13. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 9, dans lequel un constituant non soluble de l'agent retardateur de combustion est éliminé par décantation.
  14. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 13, dans lequel un alcool inférieur est mélangé dans la solution du matériau usagé de résine de styrène, libérée du constituant non soluble de l'agent retardateur de combustion par décantation, afin de faire précipiter la résine de styrène pour fixer la quantité de l'agent retardateur de combustion résiduel à au plus 1 %.
  15. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 9, dans lequel le constituant non soluble dudit agent retardateur de combustion est éliminé par une machine de centrifugation.
  16. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 15, dans lequel un alcool inférieur est mélangé dans la solution du matériau usagé de résine de styrène, libérée d'un constituant non soluble de l'agent retardateur de combustion par la machine de centrifugation, afin de faire précipiter la résine de styrène pour fixer la quantité de l'agent retardateur de combustion résiduel à au plus 1 %.
  17. Procédé de recyclage pour le matériau usagé de résine de styrène selon la revendication 9, dans lequel ledit chauffage sous vide pour éliminer les constituants volatils est réalisé à une température inférieure à 260°C.
EP00111407A 1999-05-31 2000-05-26 Méthode de recyclage de résines de styrène usagées Expired - Lifetime EP1057854B1 (fr)

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KR100711682B1 (ko) 2007-04-30
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DE60004728T2 (de) 2004-06-17
EP1057854A2 (fr) 2000-12-06

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